The present invention relates to novel pyrimidine derivatives of formula I, which have pesticidal activity, in particular fungicidal and insecticidal activity, 
wherein
A is a 5- or 6-membered ring which may be saturated or unsaturated, aromatic or non-aromatic and which may contain no hetero atoms or 1-3 hetero atoms O, S and/or N, each in the free form or in salt form; with the exception of the imidazolyl ring;
R1, R2 and R3 are each independently of the other hydrogen; halogen; C1-C8alkyl, C2-C8alkenyl or C2-C8alkinyl which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, C1-C6alkoxy, C1-C6alkylthio or C1-C6haloalkoxy; Oxe2x80x94C1-C6alkyl, Oxe2x80x94C2-C6alkenyl, Oxe2x80x94C2-C6alkynyl, Sxe2x80x94C1-C6alkyl, Sxe2x80x94C2-C6alkenyl or Sxe2x80x94C2-C6alkynyl, which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, C1-C6alkoxy or C1-C6haloalkoxy; cyano; nitro; or trimethylsilyl; provided that R1, R2 and R3 are not hydrogen at the same time;
R4 is C1-C8alkyl, C2-C8alkenyl or C2-C8alkinyl which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, cyano, nitro, COxe2x80x94C1-C4alkyl, COOxe2x80x94C1-C4alkyl, CO-aryl, COO-aryl, C1-C6alkylthio, C1-C6alkoxy or C1-C6haloalkoxy; C3-C6cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C6alkyl, C1-C6haloalkyl, halogen, cyano, C1-C6alkoxy or C1-C6haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkinyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6haloalkyl; NHR7; SR7 or OR7;
R5 is C1-C8alkyl, C2-C8alkenyl or C2-C8alkinyl which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, cyano, nitro, COxe2x80x94C1-C4alkyl, COOxe2x80x94C1-C4alkyl, CO-aryl, COO-aryl, C1-C6alkoxy, C1-C6alkylthio or C1-C6haloalkoxy; C3-C6cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C6alkyl, halogen, cyano, C1-C6alkoxy, C1-C6haloalkyl or C1-C6haloalkoxy;
R6 is hydrogen; C1-C8alkyl, C2-C8alkenyl or C2-C8alkinyl which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, cyano, nitro, COxe2x80x94C1-C4alkyl, COOxe2x80x94C1-C4alkyl, CO-aryl, COO-aryl, C1-C6alkoxy, C1-C6alkylthio or C1-C6haloalkoxy; C3-C6cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C6alkyl, halogen, cyano, C1-C6alkoxy, C1-C6haloalkyl or C1-C6haloalkoxy; Oxe2x80x94C1-C6alkyl, Oxe2x80x94C2-C6alkenyl, Oxe2x80x94C2-C6alkynyl, Sxe2x80x94C1-C6alkyl, Sxe2x80x94C2-C6alkenyl or Sxe2x80x94C2-C6alkynyl, which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, cyano, C1-C6alkoxy or C1-C6haloalkoxy; aryl or heteroaryl which are unsubstituted or mono- to tri-substituted by halogen, cyano, nitro, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or C1-C6haloalkoxy; COxe2x80x94C1-C6alkyl; COxe2x80x94C1-C6alkyl-Oxe2x80x94C1-C6alkyl; COxe2x80x94C1-C6haloalkyl; CO-heteroaryl; SO2xe2x80x94C1-C6alkyl; SO2-aryl; CO-phenyl or COxe2x80x94C1-C6alkyl-O-phenyl in which phenyl is unsubstituted or mono- to tri-substituted by halogen, cyano, nitro, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or C1-C6haloalkoxy; COOR8 wherein R8 is C1-C8alkyl, C2-C8alkenyl, C2-C8alkinyl, C3-C4cycloalkyl or phenyl which is unsubstituted or mono- to tri-substituted by halogen, cyano, nitro, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or C1-C6haloalkoxy; cyano; nitro; or halogen; and
R7 is C1-C8alkyl, C2-C8alkenyl or C2-C8alkinyl which are unsubstituted or mono- to tri-substituted by C3-C6cycloalkyl, halogen, cyano, nitro, COxe2x80x94C1-C4alkyl, COOxe2x80x94C1-C4alkyl, CO-aryl, COO-aryl, C1-C6alkoxy, C1-C6alkylthio or C1-C6haloalkoxy; C3-C6cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C6alkyl, C1-C6haloalkyl, halogen, cyano, C1-C6alkoxy or C1-C6haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkinyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6haloalkyl.
The invention also relates to the preparation of these compounds, to agrochemical compositions comprising as active ingredient at least one of these compounds, as well as to the use of the active ingredients or compositions for pest control, in particular as fungicides or insecticides, in agriculture and horticulture.
The compounds I and, optionally, all their isomers may be obtained in the form of their salts. Because the compounds I have at least one basic center they can, for example, form acid addition salts. Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid. Together with at least one acidic group, the compounds of formula I can also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal salts; or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine. Where appropriate, the formation of corresponding internal salts is also possible. Within the scope of this invention, agrochemical acceptable salts are preferred.
Where asymmetrical carbon atoms are present in the compounds of formula I these compounds are in optically active form. Owing to the presence of double bonds, the compounds can be obtained in the [E] and/or [Z] form. Atropisomerism can also occur. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.
The general terms used hereinabove and hereinbelow have the following meanings, unless otherwise defined:
Alkyl groups on their own or as structural element of other groups such as alkoxy are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl, 3-hexyl, 1-heptyl or 1-octyl.
Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, 1-pentenyl, 1-hexenyl, 1-heptenyl or 1-octenyl. Preferred alkenyl radicals contain 3 to 4 carbon atoms in the chain.
Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl, but-1-yn-3-yl, 1-pentinyl, 1-hexinyl, 1-heptinyl or 1-octinyl. The preferred meaning is propargyl.
Halogen and halo substituents will be understood generally as meaning fluorine, chlorine, bromine or iodine. Fluorine, chlorine or bromine are preferred meanings. Haloalkyl can contain identical or different halogen atoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
Cycloalkyl is, depending on the ring size, cyclopropyl, cyclobutyl, cyclopentyl, cyclohenyl, cycloheptyl or cycooctyl.
Aryl is phenyl, benzyl or naphthyl. Phenyl is preferred. Heteroaryl is pyridinyl, pyrimidinyl, triazinyl, triazolyl, thienyl, thiazolyl, oxazolyl or isoxazolyl.
Preferred compounds are those of formula I, wherein
A is phenyl, cyclohexyl, cyclopentyl, pyridyl, pyrimidinyl, thienyl[3,2-d], thienyl[2,3-d], thienyl[3,4-d], pyrazolyl, thiazolyl or furyl.
Those compounds of formula I are particularly preferred, wherein
A is phenyl;
R1, R2 and R3 are each independently of the other hydrogen; halogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1, R2 and R3 are not all hydrogen at the same time; and at least one of R1, R2 and R3 is halogen;
R4 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy;
C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy;
C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, COOC1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; COxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4haloalkyl; SO2xe2x80x94C1-C4alkyl; SO2-phenyl; COxe2x80x94C1-C4alkyl-Oxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4alkyl-O-phenyl; COOR8 wherein R8 is C1-C4alkyl or phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; nitro; or chlorine; and
R7 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup A).
Within the scope of said subgroup A, those compounds of formula I are preferred wherein
R1, R2 and R3 are each independently of the other hydrogen; chlorine or bromine; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl or Oxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1, R2 and R3 are not hydrogen at the same time; and at least one of R1, R2 and R3 is chlorine or bromine;
R4 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; or nitro; and
R7 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup A1).
Another group of compounds of formula I are preferred, wherein
A is pyridinyl;
R1, R2 and R3 are each independently of the other hydrogen; halogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1, R2 and R3 are not all hydrogen at the same time; and at least one of R1, R2 and R3 is halogen;
R4 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, COOC1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; COxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4haloalkyl; SO2xe2x80x94C1-C4alkyl; SO2-phenyl; COxe2x80x94C1-C4alkyl-Oxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4alkyl-O-phenyl; COOR8 wherein R8 is C1-C4alkyl or phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; nitro; or chlorine; and
R7 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup B).
Within the scope of subgroup B, those compounds of formula I are particularly preferred wherein
R1, R2 and R3 are each independently of the other hydrogen; chlorine or bromine; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl or Oxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1, R2 and R3 are not hydrogen at the same time; and at least one of R1, R2 and R3 is chlorine or bromine;
R4 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano or nitro; and
R7 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup B1).
A special group of compounds of formula I are preferred, wherein
A is thienyl[2,3-d];
R1 and R2 are each independently of the other hydrogen; halogen; C1-C5alkyl, C2-C5alkenyl or C2-C5 alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1 and R2 are not all hydrogen at the same time; and at least one of R1 and R2 is halogen;
R4 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, COOC1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; COxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4haloalkyl; SO2xe2x80x94C1-C4alkyl; SO2-phenyl; COxe2x80x94C1-C4alkyl-Oxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4alkyl-O-phenyl; COOR8 wherein R8 is C1-C4alkyl or phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; nitro; or chlorine; and
R7 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup C).
Within the scope of subgroup C, those compounds of formula I are preferred wherein
R1 and R2 are each independently of the other hydrogen; chlorine or bromine; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl or Oxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1 and R2 are not hydrogen at the same time; and at least one of R1 and R2 is chlorine or bromine;
R4 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; or nitro; and
R7 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup C1).
A group of compounds of formula I are preferred, wherein
A is thienyl[3,2-d];
R1 and R2 are each independently of the other hydrogen; halogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1 and R2 are not all hydrogen at the same time; and at least one of R1 and R2 is halogen;
R4 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, COOC1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; COxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4haloalkyl; SO2xe2x80x94C1-C4alkyl; SO2-phenyl; COxe2x80x94C1-C4alkyl-Oxe2x80x94C1-C4alkyl; COxe2x80x94C1-C4alkyl-O-phenyl; COOR8 wherein R8 is C1-C4alkyl or phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; nitro; or chlorine; and
R7 is C1-C5alkyl, C2-C5alkenyl or C2-C5alkinyl which are unsubstituted or mono to tri-substituted by C3-C4cycloalkyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; C3-C4cycloalkyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup D).
Within the scope of subgroup D, those compounds of formula I are preferred wherein
R1 and R2 are each independently of the other hydrogen; chlorine or bromine; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono- to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; Oxe2x80x94C1-C4alkyl, Oxe2x80x94C2-C4alkenyl or Oxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; provided that R1 and R2 are not hydrogen at the same time; and at least one of R1 and R2 is chlorine or bromine;
R4 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl or benzyl, in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl; NHR7; or OR7;
R5 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy;
R6 is hydrogen; C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; Oxe2x80x94C-C4alkyl, Oxe2x80x94C2-C4alkenyl, Oxe2x80x94C2-C4alkynyl, Sxe2x80x94C1-C4alkyl, Sxe2x80x94C2-C4alkenyl or Sxe2x80x94C2-C4alkynyl, which are unsubstituted or mono- to tri-substituted by cyclopropyl or halogen; phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; cyano; or nitro; and
R7 is C1-C4alkyl, C2-C4alkenyl or C2-C4alkinyl which are unsubstituted or mono to tri-substituted by cyclopropyl, halogen, C1-C4alkoxy, C1-C4alkylthio or C1-C4haloalkoxy; cyclopropyl which is unsubstituted or mono- to tri-substituted by C1-C4alkyl, C1-C4haloalkyl, halogen, C1-C4alkoxy or C1-C4haloalkoxy; phenyl in which the phenyl group is unsubstituted or mono- to pentasubstituted by halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, C1-C4haloalkoxy or C1-C4haloalkyl (subgroup D1).
The most preferred compounds of the invention disclosed herein are the following ones:
(6-bromo-2-propoxy-3-propyl-3H-quinazolin-4-ylidene)methylamine (cmpd.no. 1.83)
(6-chloro-2-propoxy-3-propyl-3H-quinazolin-4-ylidene)methylamine (cmpd.no. 1.74)
(6-bromo-2-butyl-3-propyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)methylamine (cmpd.no. 4.36)
(6-bromo-2-butyl-3-butyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)methylamine (cmpd.no. 4.37)
(6-chloro-2-propoxy-3-propyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)methylamine (cmpd.no. 4.29)
(6-chloro-2-butyl-3-butyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)carbamic acid methylester (cmpd.no. 4.119)
(6-chloro-2-propoxy-3-propyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)carbamic acid methylester (cmpd.no. 4.120)
N-(6-chloro-2-propoxy-3-propyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)acetamide (cmpd.no. 4.137)
N-(6-chloro-2-butyl-3-propyl-3H-thieno[2,3-d]pyrimidine-4-ylidene)acetamide (cmpd.no. 4.139).
The compounds of formula I can be prepared as follows: 
The compounds of formula I are prepared starting from an 1,2-amino-cyano compound of formula II. The cyclization (step a) in scheme 1) is conveniently carried out in the presence of POCl3, POCl3/PCl5 or SOCl2 in the presence of the amide R4CONHR5 in solvents, such as ClCH2CH2Cl, CHCl3, CH2Cl2, benzene, toluene, xylene, hexane, cyclohexane, dioxane, tetrahydrofuran, chlorobenzene or others in the temperature range from 0xc2x0 C. to reflux temperature by a reaction time of 15 min. to 18 hours. The resulting compounds III react (step b) in scheme 1) with electrophiles R6X such as alkyl-X, alkenyl-X, alkynyl-X, alkyl-SO2Cl, alkylCOCl, ClCOOalkyl, ClCOOaryl, ClCN or BrCN wherein X is a leaving group like Br, I, Cl, OTosylate, or others in the presence of a weak base such as triethylamine, Hxc3xcnig-base, pyridine, NaHCO3, Na2CO3, K2CO3 or others in solvents such as THF, dioxane, hexane, toluene, DMSO, DMF, dimethylacetamide or others at temperatures between 0xc2x0 C. and reflux-temperature during 15 min. to 48 hours. The introduction of an halogen into the ring A (step c) in scheme 1) is obtained by treating compounds of formula I with Cl2, Br2, I2, ICl,
N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, SO2Cl2 or others in a solvent like acetic acid, CH2Cl2, tert.butylmethyl ether, tetrahydrofuran, pyridine, alkylated pyridines, quinoline or others at a temperature range of 0xc2x0 C. to reflux temperature during 15 min. to 24 hours. Another possibility is the use of halogenated compounds of the formula II, when R1, R2 or R3 are halogen 
The synthesis of compounds of formula I wherein A is phenyl and R4xe2x95x90OR7 is shown in scheme 2. The corresponding aminobenzonitrile IV reacts to the compounds of formula V (step a) in scheme 2) as follows: first reacting with thiophosgene in the presence of a base like trialkylamine, NaHCO3, CaCO3, Na2CO3 or others in a solvent such as tetrahydrofurane, CHCl3/water, CH2Cl2, toluene/water or others at temperatures from 0xc2x0 to reflux during 1 to 48 hours; and second the reaction of the resulting cyanoisothiocyanate with the amine R5NH2 at temperatures of 0xc2x0 to reflux during 15 min. to 18 hours. The compounds V are then alkylated or benzylated (step b) in scheme 2) with alkyl-I, alkyl-Br or benzyl-I, benzyl-Br, benzyl-Cl in the presence of a base like NaH, KH, NaOH, Na2CO3, K2CO3 or others in a solvent such as benzene, toluene, cyclohexane, chlorbenzene, CHCl3, CH2Cl2, tetrahydrofuran, tert.butyl methyl ether, DMF or others at temperatures from 0xc2x0 to reflux during 15 min. to 24 hours. The resulting compounds VI react with 1 to 3 equivalents NaOR7 (step c) in scheme 2) in tetrahydrofuran/R7OH or pure R7OH at temperatures from 0xc2x0 to reflux during 15 min. to 24 hours. The final products are obtained by step d) in scheme 2 which is equivalent to step b) in scheme 1.
Another synthesis of compounds of formula I wherein A is phenyl, R4xe2x95x90OR7 and R6xe2x95x90C1-C4alkyl or benzyl is shown in scheme 2a. The compounds of formula V react with 2 to 5 equivalents of C1-C4alkyl-X or benzyl-X analogously to step b) in scheme 2 to the alkylated or benzylated compounds of formula Ic. The resulting compounds of formula Ic are then transformed to the compounds of formula Ia analogously step c) in scheme 2. The compounds Ic and Ia can be obtained in the E- and/or Z-form. 
Scheme 3 describes another way to obtain the compounds of formula I. Compounds of formula II react with a tetraalkylorthocarbonate ((COR7)4, step a) in scheme 3) in the absence or presence of a catalyst like p-TsOH, CF3COOH, CH3SO3H, HCl, H2SO4, HBF4, AlCl3, FeCl3, TiCl4 or others in a solvent such as CHCl3, toluene, cyclohexane, tetrahydrofuran or preferred without a solvent at temperatures from 0xc2x0 to the reflux temperature of the orthocarbonate during 15 min. to 48 hours to the compounds VII. The ring closure is carried out (step b) in scheme 3) in the presence of 1 to 30 equivalents of the amine R5NH2 where the solvent is either R5NH2 or tetrahydrofuran, tert.butylmethyl ether, toluene, benzene, dimethylformamide, dimethylsulfoxide or others at temperatures of 0xc2x0 to reflux during 15 min. to 24 hours. The resulting compounds VIII are then converted to the compounds I by step c in scheme 3 which is equivalent to step b) in scheme 1.
The compounds of the formula I can also be prepared as follows 
The compound II react with 1 to 3 equivalents of an N-alkylimidocarbonic acid dialkylester like (R7O)2Cxe2x95x90Nxe2x80x94R5 (step a in scheme 4) in a solvent such as tetrahydrofuran, tert.butylmethyl ether, toluene, dimethylformamide, dimethylsulfoxide or others in the presence of a base or an acid at temperatures from 0xc2x0 to reflux during 15 min. to 48 hours to the compounds VIII. The compounds of formula I are obtained by the steps b)-d) in scheme 4 which are analogous to the steps b)-d) in scheme 3.
The amides IX known from the literature or, for example in the case of A=phenyl, simple prepared starting from the corresponding benzoic acids, react (step a) in scheme 5) first with POCl3, POCl3/PCl5, SOCl2, CCl4/P(phenyl)3, or CBr4/P(phenyl)3 with or without solvent, preferred without, and then with 1 to 5 equivalents of R6NH2 in the presence of an additional base like triethylamine, Na2CO3 or others in a solvent such as tert.butylmethyl ether, tetrahydrofuran, toluene, xylene or others at temperatures from 0xc2x0 C. to reflux during 1 to 24 hours to the compounds X. Compounds X are hydrogenated (step b) in scheme 5) to compounds XI in the presence of a catalyst like Raney-Ni, Pd or Pt in a solvent such as tetrahydrofuran, alcohols like methanol, ethanol or others at temperatures of 0xc2x0 C. to reflux during 15 min. to 24 hours. The compounds XI, like the compounds X, can be present in their tautomeric forms XIa or XIb. Compounds of formula XI react with orthocarbonates C(OR7)4 or orthoesters like alkyl-C(OR7)3 (step c) in scheme 5) like step a) in scheme 3. Normally mixtures of isomers IA and IB are obtained. 
The invention also relates to the intermediates of formula III, V, VI, VII, VIII, X and XI, enclosing the E- and Z-isomers and their tautomeric forms 
Illustrative examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, typically benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers, typically diethyl ether, tert-butylmethyl ether, tetrahydrofuran, or dioxane; ketones, typically acetone or methyl ethyl ketone; alcohols, typically methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, typically ethyl acetate or butyl acetate; am ides, typically N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone or hexamethylphosphoric acid triamide; nitriles, typically acetonitrile; and sulfoxides, typically dimethylsulfoxide. Bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also be used as solvents or diluents. Suitable bases are, for example, alkali metal hydroxide or alkaline earth metal hydroxide, alkali metal hydride or alkaline earth metal hydride, alkali metal amide or alkaline earth metal amide, alkali metal alkanolate or alkaline earth metal alkanolate, alkali metal carbonate or alkaline earth metal carbonate, alkali metal dialkylamide or alkaline earth metal dialkylamide, or alkali metal alkylsilylamide or alkaline earth metal alkylsilylamide, alkylamines, alkylenediamines, optionally N-alkylated, optionally unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples meriting mention are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyltrimethylammonium hydroxide, and 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
The present invention also relates to novel nitrobenzamidine derivatives of formula X (when A is phenyl tautomers Xa and Xb) as intermediates, in their tautomeric forms 
and their possible isomers and mixtures of isomers and wherein R1, R2, R3, R5 and R6 have the meaning given for the compounds of formula I and wherein R5 is also hydrogen.
Formula X is understood to comprise the two tautomeric forms Xa and Xb.
The compounds X and their tautomers (Xa and Xb) or/and their E/Z-isomers may be obtained in the form of their salts. Because the compounds X (Xa and Xb) have at least one basic center they can, for example, form acid addition salts. Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid. Together with at least one acidic group, the compounds of formula X (Xa and Xb) can also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal salts or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine. Where appropriate, the formation of corresponding internal salts is also possible. Within the scope of this invention, agrochemical acceptable salts are preferred.
Where asymmetrical carbon atoms are present in the compounds of formula X (Xa and Xb), these compounds are in optically active form. Owing to the presence of double bonds, the compounds can be obtained in the [E] and/or [Z] form. Atropisomerism can also occur. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.
Preferred compounds are those of formula X, wherein
R1, R2 and R3 are each independently of the other hydrogen or halogen; and
R6 and R5 are each independently of the other hydrogen; halogen; C1-C5alkyl unsubstituted or substituted by C3-C4cycloalkyl; C2-C5alkenyl; C2-C5alkynyl; C3-C4cycloalkyl; C1-C5alkoxy; C1-C5haloalkyl; or C1-C4haloalkoxy (subgroup AA).
Within the scope of said subgroup AA, those compounds of formula X are preferred wherein
R1, R2 and R3 are each independently of the other hydrogen, chlorine, bromine or iodine;
R6 is C1-C3alkyl, OCH3, CF3, C3-C5alkenyl, C3-C4cycloalkyl or C3-C5alkynyl; and
R5 is C3-C5alkyl, C3-C5alkenyl, C3-C5alkynyl, C3-C4cycloalkyl or xe2x80x94CH2-cyclopropyl (subgroup BA).
The intermediate compounds of formula X may be prepared as follows: 
The compounds of formula X (Xa and Xb) are preferably prepared starting from the corresponding nitrobenzoic acids well known from the literature or easily synthesized by nitration of the known halobenzoic acids. The preparation of the nitrobenzoic acid chloride XIII (step a) in scheme 6) is conveniently carried out by the reaction of XII with POCl3, POCl3/PCl5 or SOCl2, in solvents, such as ClCH2CH2Cl, CHCl3, CH2Cl2, toluene, hexane, cyclohexane or others, or without solvent in the temperature range from 0xc2x0 C. to reflux temperature during 0.5 to 24 hours, in the absence or presence of a catalyst like trialkylamine or pyridine. The acid chloride XIII is then converted into the corresponding amides IX (IXa or IXb)(step b) in scheme 6) by reaction of XIII with the amine H2NR6 or the amine H2NR5 in the presence of additional bases like trialkylamine, pyridine, Na2CO3, K2CO3 or the like in a solvent such as ethers (tert.-butylmethylether, tetrahydrofuran), halohydrocarbons (CH2Cl2, CHCl3), aromatic hydrocarbons (toluene, xylene) or others in the temperature range from 0xc2x0 C. to reflux temperature during 0.5 to 24 hours. Halogenation of IX (IXa or IXb)(step c) in scheme 6) with POCl3, POCl3/PCl5, SOCl2, CCl4/P(phenyl)3 or CBr4/P(phenyl)3 in the absence or presence of catalyst like weak bases without or in the presence of solvents such as ClCH2CH2Cl, CHCl3, CH2Cl2, toluene, hexane, cyclohexane or others, in the temperature range from 0xc2x0 C. to reflux temperature during 0.5 to 24 hours, yields compounds XIV (XIVa or XIVb). The resulting compounds XIV (XIVa or XIVb) are converted to the nitrobenzamidine products X (Xa or Xb)(step d) in scheme 6) by the reaction of XIV with H2NR5 or H2NR6 in solvents such as tetrahydrofuran, dioxane, tert.-butylmethylether, hexane, toluene, cyclohexane, ClCH2CH2Cl, CHCl3, CH2Cl2, or others at temperatures between 0xc2x0 C. and reflux-temperature during 0.5 to 24 hours under possible addition of bases like trialkylamine or pyridine. 
The reactions steps a) and b) in scheme 7 corresponds to the reactions steps c) and d) in scheme 6. The reaction of intermediates XVII (step c) in scheme 7) with R5X or R6X (Xxe2x95x90Br,I), dimethyl- or diethylsulfate, ClCN, BrCN, ClCOOalkyl, NCS, NBS, NIS, alkylCOCl, alkylSO2Cl or others in the presence of a base like triethylamine, pyridine, Na2CO3, K2CO3 or the like in a solvent such tetrahydrofuran, sulfolane, dimethylformamide, dimethylsulfoxide, CHCl3, CH2Cl2, toluene, cyclohexane or others in the temperature range from 0xc2x0 C. to reflux temperature during 0.5 to 24 hours yields the compounds of formula X (Xa and Xb).
The invention also relates to the intermediate of formula XIV, namely XIVa and XIVb 
and to the intermediate XVII, namely XVIIa and XVIIb 
Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses. The compounds of formula I can be used in the agricultural sector and related fields as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic micro-organisms.
The compounds of the formula I according to the invention furthermore are valuable active compounds against insects and pests of the order Acarina such as occur on useful plants and ornamentals in agriculture and in horticulture and in forestry. The compounds of the formula I are particularly suitable for controlling pests in cotton, vegetable, fruit and rice crops, such as spider mites, aphids, butterfly caterpillars and rice cicadas. Spider mites such as Panonychus ulmi, aphids such as Aphids craccivora, butterfly caterpillars such as those of Heliothis virescens and rice cicadas such as Nilaparvata lugens or Nephotettix cincticeps may chiefly be controlled.
It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
The compounds I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Heiminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
Within the scope of this invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibber plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
Mixing components which are particularly preferred are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino-pyrimidine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatine, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, methyl 2[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3-methoxy-acrylate or 2-[{xcex1[(xcex1-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime (trifloxystrobin); dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper; nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenylamino-3,5-di-hydroimidazol-4-one (RPA 407213), 3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281), N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON 65500), 4-chloro-4-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfon-amide (IKF-916), N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)-propionamide (AC 382042) or iprovalicarb (SZX 722).
Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
A preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.
The formulation, i.e. the compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant, are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surface active compounds (surfactants).
Suitable carriers and adjuvants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners binding agents or fertilizers. Such carriers are for example described in WO 97/33890.
Further surfactants customarily employed in the art of formulation are known to the expert or can be found in the relevant literature.
The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
The following non-limitative Examples illustrate the above-described invention in more detail. Temperatures are given in degrees Celsius. The following abbreviations are used: Et=ethyl; i-propyl=isopropyl; Me=methyl; m.p.=melting point. xe2x80x9cNMRxe2x80x9d means nuclear magnetic resonance spectrum. MS=mass spectrum. xe2x80x9c%xe2x80x9d is percent by weight, unless corresponding concentrations are indicated in other units.